Agent and method for dyeing keratin fibers

ABSTRACT

The present invention relates to a fiber-dyeing agent (A) prepared by mixing two components (A1) and (A2), said agent being characterized in that component (A1) contains at least one compound of formula (I)  
                 
 
     wherein X denotes a halogen atom, a methoxy group or an ethoxy group; Y denotes an oxygen atom, a sulfur atom or a selenium atom; R1 and R2 are equal or different and independently of each other denote hydrogen, a halogen atom, a (C 1 -C 4 )-alkyl group, a halogen-substituted (C 1 -C 4 )-alkyl group, a (C 1 -C 4 )-alkoxy group, a nitro group, an acetamido group or an NR a R b  group, wherein the R a  and R b  groups are equal or different and independently of each other denote hydrogen, a (C 1 -C 4 )-alkyl group, an optionally substituted aromatic carbon ring or a (C 1 -C 4 )-alkanecarbonyl group, or R a  and R b  together with the nitrogen atom form a heterocyclic (C 3 -C 6 ) group, and component (A2) contains at least one compound from the group consisting of amines, aminonitrobenzenes and phenols; to a method for dyeing hair by use of said agent, and to a multicomponent kit.

[0001] The object of the present invention is an agent for dyeingkeratin fibers, for example silk, wool or hair, particularly human hair,and which contains a combination of (i) at least one4-nitro-2,1,3-benzoxadiazole derivative, 4-nitro-2,1,3-benzothiadiazolederivative or 4-nitro-2,1,3-benzoselenadiazole derivative and (ii) atleast one amine, aminonitrobenzene or phenol, and a method for dyeingkeratin fibers by use of said dyeing agent.

[0002] Depending on the starting color of the hair to be dyed and thedesired final result, hair colorants are divided mainly into oxidativecolorants and toners. Oxidative hair colorants are very well suited forcovering higher proportions of gray hair. The oxidative colorants usedfor a gray proportion of up to 50% are usually referred to as oxidativetoners whereas the oxidative colorants used for hair with a proportionof gray hair greater than 50%, or for “brightening”, are usuallyreferred to as oxidative colorants. Direct dyes are contained mainly innon-oxidative colorants (toners). Because of their small molecular size,some direct dyes, for example the nitro dyes, can penetrate into hairand—at least in the outer regions—dye it directly. Such toners are verygentle to the hair and as a rule can withstand six to eight hairwashings. Direct dyes, particularly nitro dyes, are also frequently usedin oxidative colorants to create certain shades or to intensify thecolor.

[0003] Nevertheless, there still exists a great need for colorantscapable of both intense and gentle coloration under mild conditions.

[0004] Surprisingly, we have now found that by use of a combination of(i) at least one-4-nitro-2,1,3-benzoxadiazole derivative,4-nitro-2,1,3-benzothiadiazole derivative or4-nitro-2,1,3-benzoselenadiazole derivative and (ii) at least one amine,aminonitrobenzene or phenol, intense colorations with a great variety ofshades can be achieved under mild conditions gentle to the hair.

[0005] Hence, the object of the present invention is an agent for dyeingfibers (A), for example wool, silk, cotton or hair and particularlyhuman hair, which is prepared by mixing two components (A1) and (A2) andis characterized in that component (A1) contains at least one compoundof formula (I)

[0006] wherein X denotes a halogen atom (F, Cl, Br, I), a methoxy groupor an ethoxy group; Y denotes an oxygen atom, a sulfur atom or aselenium atom; R1 and R2 are equal or different and independently ofeach other denote hydrogen, a halogen atom (F, Cl, Br, I), a(C₁-C₄)-alkyl group, a (C₁-C₄)-alkyl group substituted with a halogenatom (F, Cl, Br, I), a (C₁-C₄)-alkoxy group, a nitro group, an acetamidogroup or an NR^(a)R^(b) group, wherein the R^(a) and R^(b) groups areequal or different and independently of each other denote hydrogen, a(C₁-C₄)-alkyl group, an optionally substituted aromatic carbon ring or a(C₁-C₄)-alkanecarbonyl group, or R^(a) and R^(b) together with thenitrogen atom form a heterocyclic (C₃-C₆) group (for example animidazolidino, piperidino, pyrrolidino, pyrazolidino, piperazino ormorpholino group); and component (A2) contains at least one compoundselected from the group consisting of amines, aminonitrobenzenes andphenols.

[0007] Suitable compounds of formula (I) are, in particular, thefollowing 4-nitro-2,1,3-benzoxadiazoles, 4-nitro-2,1,3-benzothiadiazolesand 4-nitro-2,1,3-benzoselenadiazoles:

[0008] 4-chloro-7-nitro-2,1,3-benzoxadiazole;4-bromo-7-nitro-2,1,3-benzoxadiazole; 4-fluoro-7-nitro-2,1,3-benzoxadiazole; 4-methoxy-7-nitro-2,1,3-benzoxediazole;4-ethoxy -7-nitro-2,1,3-benzoxadiazole;4-chloro-5,7-dinitro-2,1,3-benzoxadiazole; 5,7-dichloro-4-nitro-2,1,3-benzoxadiazole; 5,7-dibromo-4-nitro-2,1,3-benzoxadiazole;7-chloro -4-nitro-5-diethylamino-2,1,3-benzoxadiazole;5-amino-7-chloro-4-nitro-2,1,3-benzoxadiazole;7-chloro-4-nitro-5-(1-piperidinyl)-2,1,3-benzoxadiazole;4-chloro-7-nitro -2,1,3-benzothiadiazole;4-bromo-7-nitro-2,1,3-benzothiadiazole; 4-methoxy-7-nitro-2,1,3-benzothiadiazole; 4-ethoxy-7-nitro-2,1,3-benzothiadiazole;4-chloro-5,7-dinitro -2,1,3-benzothiadiazole;4-bromo-5,7-dinitro-2,1,3-benzothiadiazole, 4,5-dichloro-7-nitro-2,1,3-benzothiadiazole;5,7-dichloro-4-nitro-2,1,3-benzothiadiazole;4,5-dibromo-7-nitro-2,1,3-benzothiadiazole;5,7-dibromo-4-nitro-2,1,3-benzothiadiazole;4,6-dichloro-5,7-dinitro-2,1,3-benzothiadiazole;4,6-dibromo-5,7-dinitro-2,1,3-benzothiadiazole;5-chloro-7-fluoro-4-nitro-2,1,3-benzothiadiazole; 5-anilino-7-bromo-4-nitro-2,1,3-benzothiadiazole;5-amino-7-chloro-4-nitro-2,1,3-benzothiadiazole;7-bromo-5-(diethylamino)-4-nitro-2,1,3-benzothiadiazole;4-chloro-5-methyl-7-nitro-2,1,3-benzothiadiazole;4-bromo-5-methyl-4-nitro-2,1,3-benzothiadiazole;7-bromo-5-(bromomethyl)-7-nitro-2,1,3-benzothiadiazole;N-(7-chloro-4-nitro-2,1,3-benzothiadiazole -5-yl)acetamide;4-chloro-7-nitro-2,1,3-benzoselenadiazole; 4-bromo-7-nitro-2,1,3-benzoselenadiazole; 4-methoxy-7-nitro-2,1,3-benzoselenadiazole;4-ethoxy -7-nitro-2,1,3-benzoselenadiazole;5,7-dibromo-4-nitro-2,1,3-benzoselenadiazole;5,7-dichloro-4-nitro-2,1,3-benzoselenadiazole;7-bromo-5-methyl-4-nitro-2,1,3-benzoselenadiazole and7-bromo-5-(bromomethyl)-4-nitro-2,1,3-benzoselenadiazole, among whichthe following compounds are particularly preferred:

[0009] 4-chloro-7-nitro-2,1,3-benzoxadiazole;4-bromo-7-nitro-2,1,3-benzoxadiazole; 4-chloro-7-nitro-2,1,3-benzothiadiazole; 4-bromo-7-nitro-2,1,3-benzothiadiazole;4-chloro-7-nitro -2,1,3-benzoselenadiazole and4-bromo-7-nitro-2,1,3-benzoselenadiazole.

[0010] Some of the compounds of formula (I) are commercially available.The compounds of formula (I), however, can also be prepared by methodsof synthesis known from the literature, for example as described in theJournal of Organic Chemistry 36 (1), pages 207-209 (1971); Recueil Trav.Chim. Pays-Bas 86 (12), pages 1159-1181 (1967); Journal of MedicinalChemistry, vol 17 (2), pages 203-206 (1974); Journal of the ChemicalSociety (B), 1967, pages 909-911 or in U.S. Pat. No. 3,577,427.

[0011] Suitable amines are aliphatic or aromatic (isocyclic orheterocyclic) compounds with at least one amino group. Suitableaminonitrobenzenes are aromatic (isocyclic or heterocyclic) compoundswith at least one nitro group and at least one amino group, and suitablephenols are aromatic (isocyclic or heterocyclic) compounds with at leastone hydroxyl group. Examples of the amines, aminonitrobenzenes andphenols contained in component (A2) are, in particular, the following:

[0012] ethanolamine; propylamine; 3-amino-1-propanol; butylamine;4-amino-1-butanol; 1,4-diaminobenzene (p-phenylenediamine);1,4-diamino-2-methylbenzene (p-toluylenediamine);1,4-diamino-2,6-dimethylbenzene; 1,4-diamino-3,5-diethylbenzene;1,4-diamino -2,5-dimethylbenzene; 1,4-diamino-2,3-dimethylbenzene;2-chloro-1,4-diaminobenzene; 2,5-diaminobiphenyl;1,4-diamino-2-hydroxymethylbenzene; 1,4-diamino-2-(2-hydroxyethoxy)benzene;2-[2-(acetylamino)ethoxy]-1,4-diaminobenzene; N-methylaniline;4-phenylaminoaniline; 4-dimethylaminoaniline; 4-diethylaminoaniline;4-dipropylaminoaniline; 4-[ethyl(2-hydroxyethyl)amino]aniline;4-[di(2′-hydroxyethyl)amino]aniline;4-[di(2-hydroxyethyl)amino]-2-methylaniline;4-[(2′-methoxyethyl)amino]aniline; 4-[(3′-hydroxypropyl)amino]aniline;4-[(2,3-dihydroxypropyl)amino]aniline;1,4-diamino-2-(2′-hydroxyethyl)benzene;1,4-diamino-2-(1′-hydroxyethyl)benzene;1,4-diamino-2-(1′-methylethyl)benzene;1,4-diamino-2-(methoxymethyl)benzene;1,4-diamino-2-(aminomethyl)benzene; 1,3-bis-[(4′-aminophenyl)(2′-hydroxyethyl)amino]-2-propanol;1,4-bis-[(4-aminophenyl)amino]butane;1,8-bis-(2′,5′-diaminophenoxy)-3,6-dioxaoctane; phenol; hydroquinone;2-methylphenol; 3-methylphenol; 4-methylphenol;5-methyl[-2-(1′-methylethyl)phenol; 4-aminophenol;4-amino-3-methylphenol; 4-amino-3-(hydroxymethyl)phenol; 4-amino-3-fluorophenol; 4-methylaminophenol; 4-amino-2-(aminomethyl)phenol;4-amino-2-(hydroxymethyl)phenol; 4-amino-2-fluorophenol;4-amino-[(2′-hydroxyethyl)amino]-methylphenol; 4-amino-2-methylphenol;4-amino-2-(methoxymethyl)phenol; 4-amino -2-(2′-hydroxyethyl)phenol;5-aminosalicylic acid; 2,5-diaminopyridine;2,4,5,6-tetraaminopyrimidine; 2,5,6-triamino-4-(1H)-pyrimidone;4,5-diamino-1-(4′-methyl-benzyl) -1H-pyrazole; 4,5-diamino-1H-pyrazole;4,5-diamino-1-(4′-methoxybenzyl) -1H-pyrazole;4,5-diamino-1-(3′-methoxybenzyl)-1H-pyrazole;4,5-diamino-1-(4′-chlorobenzyl) -1H-pyrazole;4,5-diamino-1-(4′-methylphenyl)-1H-pyrazole;4,5-diamino-1-(4′-methoxyphenyl)-1H-pyrazole;4,5-diamino-1-(3′-methoxyphenyl)-1H-pyrazole;4,5-diamino-1-(4′-chlorophenyl)-1H-pyrazole;4,5-diamino-1-(2′-hydroxyethyl)-1H-pyrazole;4,5-diamino-1-methyl-1H-pyrazole; 4,5-diamino-1-ethyl-1H-pyrazole;4-amino -1-[(4′-methoxyphenyl)methyl]-5-(methylamino)-1H-pyrazole;4-amino-5-[(2′-hydroxyethyl)amino]-1-(phenylmethyl)-1H-pyrazole;4,5-diamino-1-methyl-3-phenyl -1H-pyrazole;4,5-diamino-1-(2′-hydroxyethyl)-3-phenyl-1H-pyrazole; 4,5-diamino-1,3-dimethyl-1H-pyrazole; 4,5-diamino-3-methyl-1-phenyl-1H-pyrazole;4,5-diamino-1-(1-isopropyl)-1H-pyrazole; 2-aminophenol;2-amino-6-methylphenol; 2-amino-5-methylphenol;1,4-diamino-2-(thiophen-2-yl)benzene;1,4-diamino-2-(thiophen-3-yl)benzene;1,4-diamino-2-(pyridin-3-yl)benzene; 1,2,4-trihydroxybenzene;N-(3-dimethylaminophenyl)urea; 2,6-diaminopyridine;2-amino-4-[(2′-hydroxyethyl)-amino]anisole;2,4-diamino-1-fluoro-5-methylbenzene;2,4-diamino-1-methoxy-5-methylbenzene;2,4-diamino-1-ethoxy-5-methylbenzene; 2,4-diamino-1-(2′-hydroxyethoxy)-5-methylbenzene; 2,4-di-[(2′-hydroxyethyl)amino]-1,5-dimethoxybenzene;2,3-diamino -6-methoxypyridine;3-amino-6-methoxy-2-(methylamino)pyridine; 2,6-diamino-3,5-dimethoxypyridine; 3,5-diamino-2,6-dimethoxypyridine;1,3-diaminobenzene (m-phenylenediamine);2,4-diamino-1-(2′-hydroxyethoxy)benzene;2,4-diamino-1,5-di(2′-hydroxyethoxy)benzene;1,3-diamino-4-(2,3-dihydroxypropoxy)benzene; 1,3-diamino-4-(3-hydroxypropoxy)benzene; 1,3-diamino-4-(2-methoxyethoxy)benzene;1-(2′-aminoethoxy)-2,4-diaminobenzene;2-amino-i-(2′-hydroxyethoxy)-4-methylaminobenzene;2,4-diaminophenoxyacetic acid; 3-[di(2′-hydroxyethyl)amino]aniline;4-amino-2-di[(2′-hydroxyethyl)amino]-1-ethoxybenzene;5-methyl-2-(1-methylethyl)phenol; 3-[(2′-hydroxyethyl)amino]aniline;3-[(2′-aminoethyl)amino]aniline; 1,3-2′,4′-diaminophenoxy)propane;di(2′,4′-diaminophenoxy)methane; 1,3-diamino-2,4-dimethoxybenzene;2,6-bis-(2′-hydroxyethyl)aminotoluene; 4-hydroxyindole;3-dimethylaminophenol; 3-diethylaminophenol; 5-amino-2-methylphenol;5-amino-4-fluoro-2-methylphenol; 5-amino-4-methoxy-2-methylphenol;5-amino-4-ethoxy-2-methylphenol; 3-amino-2,4-dichlorophenol;5-amino-2,4-dichlorophenol; 3-amino-2-methylphenol;3-amino-2-chloro-6-methylphenol; 3-aminophenol;N-[(3′-hydroxyphenyl)amino]acetamide;5-[(2-hydroxyethyl)amino-2-methylphenol;5-[(2-hydroxyethyl)amino]-4-methoxy -2-methylphenol;3-[(2′-hydroxyethyl)amino]phenol; 3-[(2′-methoxyethyl)-amino]phenol;5-amino-2-ethylphenol; 5-amino-2-methoxyphenol;2-(4′-amino-2′-hydroxyphenoxy)ethanol;5-[(3′-hydroxypropyl)amino]-2-methylphenol;3-[(2′,3′-dihydroxy)propylamino]-2-methylphenol;3-[(2′-hydroxyethyl)amino]-2-methylphenol; 2-amino-3-hydroxypyridine;2,6-dihydroxy-3,4-dimethylpyridine; 5-amino-4-chloro -2-methylphenol;1-naphthol; 1,5-dihydroxynaphthalene; 1,7-dihydroxynaphthalene;2,3-dihydroxynaphthalene; 2,7-dihydroxynaphthalene; 2-methyl-1-naphtholacetate; 1,3-dihydroxybenzene (resorcinol);1-chloro-2,4-dihydroxybenzene; 2-chloro-1,3-dihydroxybenzene;1,2-dichloro-3,5-dihydroxy-4-methylbenzene;1,5-dichloro-2,4-dihydroxybenzene; 1,3-dihydroxy-2-methylbenzene;3,4-methylenedioxyphenol; 3,4-methylenedioxyaniline;5-[(2′-hydroxyethyl)amino]-1,3-benzodioxole; 6-bromo-1-hydroxy-3,4-methylenedioxybenzene; 3,4-diaminobenzoic acid;3,4-dihydro-6-hydroxy -1,4(2H)-benzoxazine;6-amino-3,4-dihydro-1,4(2H)-benzoxazine; 3-methyl-1-phenyl-5-pyrazolone; 5,6-dihydroxyindole; 5,6-dihydroxyindoline;5-hydroxyindole; 6-hydroxyindole; 7-hydroxyindole and 2,3-indolindione;1,4-bis-[2′-hydroxyethyl)amino]-2-nitrobenzene;1-(2′-hydroxyethyl)-amino-2-nitro-4-[di(2′-hydroxyethyl)amino]benzene;1-amino-3-methyl-4-[(2′-hydroxyethyl)amino]-6-nitrobenzene;4-[ethyl-(2′-hydroxyethyl)amino]-1-[(2′-hydroxyethyl)amino]-2-nitrobenzenehydrochloride;4-[di(2′-hydroxyethyl)amino]-1-[(2′-methoxyethyl)amino]-2-nitrobenzene;1-[(2′,3′-dihydroxypropyl)amino]-4-methyl-(2′-hydroxyethyl)amino]-2-nitrobenzene;1-[(2′,3′-dihydroxypropyl)amino]-4-ethyl-(2′-hydroxyethyl)amino]-2-nitrobenzenehydrochloride; 1-(3′-hydroxypropylamino)-4-[(di-(2′-hydroxyethyl)amino]-2-nitrobenzene; 1-methylamino-4-[methyl-(2′,3′-dihydroxypropyl)amino]-2-nitrobenzene;2-[(4-amino-2-nitrophenyl)-amino]-5-dimethylaminobenzoic acid;1-(2′-aminoethylamino)-4-[(di(2′-hydroxyethyl)-amino]-2-nitrobenzene;1-amino-4-[(2′-hydroxyethyl)amino]-2-nitrobenzene;2-amino-4,6-dinitrophenol; 1,4-diamino-2-nitrobenzene;4-amino-2-nitrodiphenylamine;1-amino-4-[(di(2′-hydroxyethyl)amino]-2-nitrobenzene hydrochloride;1-amino-5-chloro -4-[(2′-hydroxyethyl)amino]-2-nitrobenzene;4-amino-1-[(2′-hydroxyethyl)amino]-2-nitrobenzene;4-[(2′-hydroxyethyl)methylamino]-1-(methylamino)-2-nitrobenzene; 1-amino-4-[(2′,3′-dihydroxypropyl)amino]-5-methyl-2-nitrobenzene;1-amino-4-(methylamino) -2-nitrobenzene;4-amino-2-nitro-1-[(prop-2-en-1-yl)amino]benzene; 4-amino-3-nitrophenol;4-[(2′-hydroxyethyl)amino]-3-nitrophenol;4-[(2-nitrophenyl)amino]phenol;1-[(2′-aminoethyl)amino]-4-(2′-hydroxyethoxy)-2-nitrobenzene;4-(2′,3′-di-hydroxypropoxy) -1-[(2′-hydroxyethyl)amino]-2-nitrobenzene;1-amino-5-chloro-4-[(2′,3′-dihydroxypropyl)amino]-2-nitrobenzene;5-chloro-1,4-[di-(2′,3′-dihydroxypropyl)amino]-2-nitrobenzene;2-[(2′-hydroxyethyl)amino]-4,6-dinitrophenol; 4-ethylamino-3-nitrobenzoic acid; 2-[(4′-amino-2′-nitrophenyl)amino]benzoic acid;2-chloro-6-ethylamino -4-nitrophenol; 2-amino-6-chloro-4-nitrophenol;4-[(3′-hydroxypropyl)-amino]-3-nitrophenol; 2,5-diamino-6-nitropyridine;6-amino-3-[(2′-hydroxyethyl)amino]-2-nitropyridine;3-amino-6-[(2′-hydroxyethyl)amino]-2-nitropyridine;3-amino-6-(ethylamino)-2-nitropyridine;3-[(2′-hydroxyethyl)amino]-6-(methylamino)-2-nitropyridine;3-amino-6-(methylamino)-2-nitropyridine;6-(ethylamino)-3-[(2′-hydroxyethyl)amino]-2-nitropyridine;1,2,3,4-tetrahydro-6-nitro-quinoxaline; 7-amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazine; 1,2-diamino-4-nitrobenzene;1-amino-2-[(2′-hydroxyethyl)-amino]-5-nitrobenzene;1-(2′-hydroxyethoxy)-2-[(2′-hydroxyethyl)amino]-5-nitrobenzene;1-[(2′-hydroxyethyl)amino]-2-nitrobenzene;2-(di(2′-hydroxyethyl)amino]-5-nitrophenol;2-[(2′-hydroxyethyl)amino]-1-methoxy-5-nitrobenzene;2-amino-3-nitrophenol; 1-amino-2-methyl-6-nitrobenzene;1-(2′-hydroxyethoxy)-3-methylamino-4-nitrobenzene;2,3-(dihydroxypropoxy)-3-methylamino-4-nitrobenzene;2-[(2′-hydroxyethyl)amino]-5-nitrophenol;3-[(2′-aminoethyl)amino]-1-methoxy-4-nitrobenzene hydrochloride;1-[(2′-ureidoethyl)amino]-4-nitrobenzene;4-[(2′,3′-dihydroxypropyl)-amino]-3-nitro-1-trifluoromethylbenzene;1-chloro-2,4-bis-[(2′-hydroxyethyl)amino]-5-nitrobenzene;1-amino-4-[(2′-aminoethyl)amino]-5-methyl-2-nitrobenzene;4-[(2′-hydroxyethyl)amino]-3-nitro-1-methylbenzene;1-chloro-4-[(2′-hydroxyethyl)amino]-3-nitrobenzene;4-[(2′-hydroxyethyl)amino]-3-nitro-1-trifluoromethylbenzene;4-[(2′-hydroxyethyl)amino]-3-nitrobenzonitrile;4-[(2′-hydroxyethyl)amino]-3-nitrobenzamide;3-[(2′-hydroxyethyl)amino]-4-methyl-1-nitrobenzene and4-chloro-3-[(2′-hydroxyethyl)amino]-1-nitrobenzene.

[0013] Particularly preferred amines, aminonitrobenzenes or phenols areethanolamine, 1,4-diaminobenzene; 1,4-diamino-2-methylbenzene;1,4-diamino-2-(2′-hydroxyethyl)-benzene;1,4-diamino-2-(1′-hydroxyethyl)benzene;2,4-diamino-1-(2′-hydroxyethoxy)benzene; 2,4,5,6-tetraaminopyrimidine;hydroquinone; 5,6-diamino-2,4-dihydroxy-pyrimidine; 2,7-diaminofluorene;1-amino-2-naphthol; 2,3-dihydro-3-methyl-2-benzothiazolone hydrazone;2-aminophenol; 4,5-diamino-1-(2′-hydroxyethyl)-1H-pyrazole;4,5-diamino-1-benzyl-1H-pyrazole; phenol;4,5-diamino-1-[(4′-methylbenzyl)-1H-pyrazole; 4,5-diamino-1H-pyrazole;4,5-diamino-1-methyl-1H-pyrazole; 4,5-diamino-(1-isopropyl)-1H-pyrazole; N-(3-dimethylaminophenyl)urea;2-amino-4-[(2′-hydroxyethyl)amino]anisole; 1,3-diaminobenzene;1,3-di[(2,4-diaminophenoxy)propane; 4-methylphenol; 4-aminophenol;4-amino-3-methylphenol; 5-amino-2-methylphenol; 3-aminophenol;1,3-dihydroxybenzene; 5-hydroxyindole;4-[(2′-hydroxyethyl)amino]-3-nitro -1-methylbenzene;4-[(2′-hydroxyethyl)amino]-3-nitrophenol; 2-amino-6-chloro-4-nitrophenol; 2-chloro-6-ethylamino-4-nitrophenol;1-amino-2-[(2′-hydroxyethyl)-amino]-5-nitrobenzene as well as the2,5-diaminonitrobenzenes, for example 1-(2′-hydroxyethyl)amino-2-nitro-4-[(di(2′-hydroxyethyl)amino]benzene,1-amino-4-[di(2′-hydroxyethyl)amino]-2-nitrobenzene;4-[di(2′-hydroxyethyl)amino]-1-[(2′-methoxyethyl)amino]-2-nitrobenzene;4-[ethyl-(2′-hydroxyethyl)amino]-1-[(2′-hydroxy-ethyl)amino]-2-nitrobenzene;1-amino-5-chloro-4-[(2′,3′-dihydroxypropyl)amino]-2-nitrobenzene and2,5-diamino-6-nitropyridine.

[0014] The compounds of formula (I) and the amines, aminonitrobenzenesor phenols are kept separate from each other and are mixed with eachother shortly before use. If the compounds of formula (I) and theamines, aminonitrobenzenes and/or phenols are solids, however, it isalso possible to package them together and to prepare the ready-for-usecolorant (A) shortly before use by mixing the compounds of formula (I)and the amines, aminonitrobenzenes and/or phenols with water or with aliquid preparation containing the remaining constituents of the coloringagent.

[0015] Moreover, In addition to the compounds of formula (I) and to theamines, aminonitrobenzenes and phenols, the colorant of the inventioncan optionally contain in component (A2) and in the ready-for-usepreparation (A) other common, physiologically innocuous, direct dyesfrom the group consisting of cationic and anionic dyes, disperse dyes,azo dyes, quinone dyes and triphenylmethane dyes.

[0016] These direct dyes can be used in component (A2) in a total amountfrom about 0.02 to about 20 wt. % and preferably from 0.2 to 10 wt. %,the total amount of direct dyes in the ready-for-use colorant (A)obtained by mixing components (A1) and (A2) being about 0.01 to about 10wt. % and preferably 0.1 to 5 wt. %.

[0017] As a rule, the coloring agent of the invention consists of amixture of components (A1) and (A2), namely of a dye carrier composition(A1) which contains the compound of formula (I), and an additional dyecarrier composition (A2) which contains the amines, aminonitrobenzenesand/or phenols.

[0018] The compounds of formula (I) and the amines, aminonitrobenzenesand/or phenols are contained in their respective dye carrier composition[component (A1) or component (A2)] in a total amount from about 0.02 toabout 20 wt. % and preferably from about 0.2 to about 10 wt. %, thecompounds of formula (I) and the amines, aminonitrobenzenes and/orphenols being contained in the ready-for-use coloring agent (A) in atotal amount from about 0.01 to about 10 wt. % and preferably from about0.1 to about 5 wt. %.

[0019] Components (A1) and (A2) and the ready-for-use coloring agent (A)can be prepared in the form of a solution, particularly an aqueous oraqueous-alcoholic solution, or as a cream, a gel or an emulsion. Such apreparation consists of a mixture of the compound of formula (I) and ofthe amines, aminonitrobenzenes and/or phenols with the additivescommonly used in such preparations.

[0020] Common additives for colorants used in the form of solutions,creams, emulsions, gels or aerosol foams are, for example, solvents suchas water, the lower aliphatic alcohols, for example ethanol, n-propanoland isopropanol, or the polyols such as glycerol and 1,2-propandiol,moreover wetting agents or emulsifiers from the classes of anionic,cationic, amphoteric or nonionic surface-active substances such as thefatty alcohol sulfates, ethoxylated fatty alcohol sulfates,alkylsulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts,alkylbetaines, ethoxylated fatty alcohols*¹, ethoxylated nonylphenols*,fatty alkanolamides*, ethoxylated fatty esters, moreover thickeners suchas the higher fatty alcohols, starch or cellulose derivatives, perfumes,hair-pretreatment agents, conditioners, hair swelling agents,preservatives, furthermore vaselines, paraffin oils and fatty acids aswell as hair-care agents such as cationic resins, lanolin derivatives,cholesterol, pantothenic acid and betaine. The said constituents areused in amounts commonly employed for such purposes, for example thewetting agents and emulsifiers at a concentration of about 0.5 to about30 wt. % [always based on component (A1) or (A2)], the thickeners in anamount from about 0.1 to about 25 wt. % [always based on component (A1)or component (A2)], and the hair-care agents at a concentration of about0.1 to about 5.0 wt. % [always based on component (A1) or component(A2)].

[0021] The pH of the ready-for-use colorant (A) is about 3 to about 12and preferably about 4 to about 10 and as a rule is reached upon mixingcomponent (A1) with component (A2). To adjust the pH of components (A1)and (A2) and of the ready-for-use colorant (A) to the value desired forthe dyeing, an alkalinizing agent can be used if needed, for example analkali metal hydroxide, alkaline earth metal hydroxide, alkali metalacetate, alkaline earth metal acetate, alkali metal carbonate oralkaline earth metal carbonate, or an acid, for example lactic acid,acetic acid, tartaric acid, phosphoric acid, hydrochloric acid, citricacid, ascorbic acid or boric acid.

[0022] The ready-for-use colorant is prepared just before use by mixingcomponents (A1) and (A2), optionally by adding a base, for examplesodium acetate, sodium bicarbonate or sodium carbonate, and is thenapplied to the fibers, particularly human hair. Depending on the depthof shade desired, this mixture is allowed to act for about 5 to about 60minutes and preferably from about 15 to about 30 minutes at atemperature of about 20 to about 50° C. and particularly from about 30to about 40° C. The fibers are then rinsed with water, optionally washedwith a shampoo and then dried.

[0023] Another object of the present invention is a multicomponent kitconsisting of a preparation of component (A1), a preparation ofcomponent (A2) and optionally an agent for adjusting the pH. Thepreparations of components (A1) and (A2) can, of course, also consistsof several individual components which are mixed just before use. A2-component kit is also possible, in which case the first componentconsists of a powder of a compound of formula (I), the amine,aminonitrobenzene and/or phenol and optionally other common powderedcosmetic additives, and the second component is water or a liquidcosmetic preparation. Particularly preferred, however, is a 2-componentkit consisting of a preparation of component (A1) and a preparation ofcomponent (A2).

[0024] The coloring agent of the invention imparts to the fibers,particularly keratin fibers such as human hair, in a gentle manner, auniform and long-lasting coloration, a wide range of yellow todark-violet or brown-black color shades being possible.

[0025] Because of their high resistance to oxidants, the compounds ofgeneral formula (I) can also be used in oxidative colorants based onoxidation dye precursors. It is also possible to use the compounds ofgeneral formula (I) in brightening toners in which—for the purpose ofbrightening the hair to be dyed or of improving its luster—the directdyes are used in combination with an oxidant.

[0026] The following examples illustrate the object of the inventionwithout limiting its scope.

EXAMPLES Examples 1 to 21

[0027] Hair Colorants Component (A1) 0.5 g of7-chloro-4-nitro-2,1,3-benzoxadiazole 5.0 g of ethanol 4.0 g of decylpolyglucoside (aqueous solution; Plantaren ® 2000, supplied by Cognis,Germany) 0.2 g of disodium ethylenediaminetetraacetate hydrate to 100.0g water, demineralized Component (A2) X g of powdered amine and/orphenol as per Table 1.

[0028] The aforesaid mixture [component (A1)] was mixed uniformly withthe powder containing the amine or the phenol [component (A2)] at roomtemperature (20-25° C.) or with slight heating (35-40° C.)—optionally byadding a spatula tip-full of sodium acetate. If necessary, the pH wasadjusted to the desired value with sodium hydroxide or citric acid.

[0029] The ready-for-use hair colorant thus obtained was applied to thehair and uniformly distributed with a brush. After an exposure time of30 min at 40° C., the hair was rinsed with lukewarm water and thendried.

[0030] The amount of amine or phenol used and the resulting colorationsare summarized in the following Table 1. TABLE 1 Ex- ample Amine orPhenol Shade After Color values No. Used (amount in g) pH Dyeing L a b 1ethanolamine 9.3 yellow +41.16 +11.42 +43.41 (0.153 g) 2 phenol (0.235g) 3.5 yellow +57.82 +8.43 +62.90 3 hydroquinone 7.0 orange +69.52 +2.72+46.43 (0.275 g) 4 4-dimethylamino- 4.6 violet +31.83 +13.15 −2.80aniline (0.340 g) 5 1,4-diaminobenzene 4.7 violet +26.36 +23.37 −0.48(0.270 g) 6 1,4-diamino-2- 4.5 violet +30.81 +21.60 +0.28methylbenzene.HCl (0.055 g) 7 1,4-diamino-2-(2- 3.9 violet +21.33 +17.74+2.16 hydroxyethyl)- benzene sulfate (0.630 g) 8 4-aminophenol 3.4ruby-red +26.13 +39.62 +15.48 (0.273 g) 9 2,4,5,6-tetraamino- 9.8green-brown +34.85 +4.30 +18.31 pyrimidine sulfate (0.640 g) 105,6-diamino-2,4-di- 7.3 brown-orange +32.73 +15.18 +28.79hydroxypyrimidine sulfate (0.455 g) 11 4,5-diamino-1-(2′- 9.3 red +29.07+38.14 +22.13 hydroxyethyl)-1H- pyrazole sulfate (0.600 g) 122,7-diaminofluorene 7.4 violet +26.95 +18.76 +5.13 (0.490 g) 131-amino-2-naphthol. 6.3 brown +41.52 +7.03 +20.43 HCl (0.489 g) 142,3-dihydro-3-methyl- 6.4 orange +44.00 +40.62 +46.52 2-benzothiazolonehydrazone.HCl (0.584 g) 15 N-(3-dimethylamino- 6.5 yellow-brown +35.42+1.75 +14.81 phenyl)urea (0.448 g) 16 2-amino-4-[(2′-hy- 6.7 gray +47.79−2.78 +1.60 droxyethyl)amino]- anisole sulfate (0.746 g) 171,3-diaminobenzene 4.3 red-violet +32.31 +18.33 +11.25 (0.270 g) 182,4-diamino-1-(2′- 4.1 blue-violet +26.41 +4.77 −2.69 hydroxyethoxy)ben-zene sulfate (0.666 g) 19 5-amino-2-methyl- 4.5 ruby-red +32.96 +39.20+24.27 phenol (0.308 g) 20 3-aminophenol 4.4 ruby-red +38.98 +40.37+34.32 (0.273 g) 21 1,3-dihydroxy- 4.0 yellow +70.64 +8.37 +47.07benzene (0.275 g)

Examples 22 to 28

[0031] Hair Colorants Component (A1): 1.0 g of7-chloro-4-nitro-2,1,3-benzoxadiazole 5.0 g of ethanol 4.0 g of decylpolyglucoside (Plantaren ® 2000), aqueous solution 0.2 g of disodiumethylenediaminetetraacetate hydrate to 100.0 g water, demineralizedComponent (A2): X g of amine or phenol as per Table 2 5.0 g of ethanol4.0 g of decyl polyglucoside (Plantaren ® 2000), aqueous solution 0.2 gof disodium ethylenediaminetetraacetate hydrate to 100.0 g water,demineralized

[0032] 10 g of component (A1) was mixed uniformly with 10 g of component(A2) at room temperature (20-25° C.) or with slight heating (35-40°C.)—optionally by adding a spatula tip-full of sodium acetate. Ifnecessary, the pH was adjusted to the desired value with sodiumhydroxide or citric acid.

[0033] The ready-for-use hair colorant thus obtained was applied to thehair and uniformly distributed with a brush. After an exposure time of30 min at 40° C., the hair was rinsed with lukewarm water and thendried.

[0034] The amount of amine or phenol used and the resulting colorationsare summarized in the following Table 2. TABLE 2 Ex- ample Amine orPhenol Shade After Color values No. Used (amount in g) pH Dyeing L a b22 1,4-diaminobenzene 4.8 violet +21.77 +20.65 +0.80 (0.540 g) 6.8+26.66 +25.47 −1.39 9.8 +30.48 +24.70 −0.35 23 1,4-diamino-2- 4.7 violet+21.69 +19.99 +3.57 methylbenzene 6.8 +29.24 +22.23 +5.84 sulfate (1.100g) 10.0 +30.14 +19.04 +4.62 24 4-aminophenol 4.6 ruby-red +23.87 +35.97+13.01 (0.546 g) 6.9 +25.30 +39.15 +14.64 9.5 +23.31 +35.70 +12.80 252-aminophenol 4.8 red-orange +34.39 +40.22 +29.97 (0.546 g) 6.6 +34.59+39.94 +30.89 9.2 +32.15 +34.18 +38.30 26 phenol 4.7 yellow +67.34 +6.41+76.05 (0.470 g) 6.8 +62.29 +9.85 +73.75 9.8 +68.61 +4.33 +70.47 27phenol (0.234 g) 4.3 pink-violet +43.82 +22.25 +12.60 and 1,4-diamino-2-7.7 +47.73 +20.71 +8.74 methylbenzene sul- 10.0 +37.17 +20.80 +2.67 fate(0.550 g) 28 2-aminophenol 4.4 ruby-red +23.96 +35.28 +13.08 (0.272 g)and 7.7 +21.82 +30.59 +10.46 4-aminophenol 9.5 +21.95 +27.56 +10.03(0.272 g)

Examples 29 and 30

[0035] Hair Colorants in Cream Form Component (A1):  1 g of7-chloro-4-nitro-2,1,3-benzoxadiazole 12 g of cetearyl alcohol 10 g oflauryl ether sulfate, 28% aqueous solution 20 g of ethanol to 100 gwater, demineralized

[0036] The cetearyl alcohol was melted at 80° C. The lauryl ethersulfate was heated to 80° C. with 95% of the water and added to themolten cetearyl alcohol. The mixture was stirred until a cream formed.The 7-chloro-4-nitro-2,1,3-benzoxadiazole was mixed with the ethanol andthe remainder of the water at room temperature and the resulting mixturewas added to the cream. The pH of the cream thus obtained was 4.6.Component (A2) X g of the amine or phenol as per Table 3 12 g ofcetearyl alcohol 10 g of lauryl ether sulfate, 28% aqueous solution 20 gof ethanol to 100 g water, demineralized

[0037] The cetearyl alcohol was melted at 80° C. The lauryl ethersulfate was heated to 80° C. with 95% of the water and added to themolten cetearyl alcohol. The mixture was stirred until a cream formed.The amine or the phenol was mixed with the h ethanol and the remainderof the water at room temperature, and the resulting mixture was added tothe cream. The pH of the cream thus obtained was adjusted to 7(optionally with addition of sodium acetate).

[0038] Components (A1) and (A2) were mixed with one another in a 1:1ratio. Optionally a spatula tip-full of sodium acetate was added. Ifneeded, the pH of the ready-for-use colorant was adjusted to the desiredvalue with sodium hydroxide or citric acid. The resulting ready-for-usehair colorant was applied to the hair and uniformly distributed with abrush. After an exposure time of 30 min at 40° C., the hair was washedwith a shampoo, rinsed with lukewarm water and then dried.

[0039] The amount of amine or phenol used and the resulting colorationsare summarized in the following Table 3. TABLE 3 Ex- ample Amine orPhenol Shade After Color values No. Used (amount in g) pH Dyeing L a b29 1,4-diaminobenzene 7.2 violet +20.8 +20.3 +1.4 (1.350 g) 304-aminophenol 7.3 ruby-red +22.4 +35.7 +11.4 (1.370 g)

Examples 31 to 42

[0040] Hair Colorants Component (A1) 1.0 g of7-chloro-4-nitro-2,1,3-benzoxadiazole 5.0 g of ethanol 4.0 g of decylpolyglucoside (aqueous solution; Plantaren ® 2000, supplied by Cognis,Germany) 0.2 g of disodium ethylenediaminetetraacetate hydrate to 100.0g water, demineralized Component (A2) X g of aminonitrobenzene as perTable 4 5.0 g of ethanol 4.0 g of decyl polyglucoside (Plantaren ®2000), aqueous solution 0.2 g of disodium ethylenediaminetetraacetatehydrate to 100.0 g water, demineralized

[0041] 10 g of component (A1) was mixed uniformly with 10 g of component(A2) at room temperature (20-25° C.) or with slight heating (35-40°C.)—optionally by adding a spatula tip-full of sodium acetate. Ifnecessary, the mixture was heated at 40 to 60° C. for 15 minutes. Whenneeded, the pH was adjusted to the desired value with sodium hydroxideor citric acid.

[0042] The ready-for-use hair colorant thus obtained was applied to thehair and uniformly distributed with a brush. After an exposure time of30 min at 40° C., the hair was rinsed with lukewarm water and thendried.

[0043] The amount of aminonitrobenzene used and the resultingcolorations are summarized in the following Table 4. TABLE 4 Ex- ampleAminonitrobenzene Shade After Color values No. Used (amount in g) pHDyeing L a b 31 1-(2′-hydroxyethyl)- 6.3 brown-black +17.19 +3.94 +2.43amino-2-nitro-4-[(di- with violet (2′-hydroxyethyl)- reflexesamino]benzene (1.420 g) 32 4-di[(2′-hydroxy- 4.9 brown-black +18.47+5.56 +3.59 ethyl)amino]-1- with violet [(2-methoxyethyl)- reflexesamino]-2-nitro- benzene (1.490 g) 33 4-[ethyl-(2′-hydroxy- 5.4brown-black +18.27 +3.45 +2.71 ethyl)amino]-1-[(2′- with violethydroxyethyl)amino]- reflexes 2-nitrobenzene.HCl (1.520 g) 341-amino-4-[di(2′- 5.2 brown with +18.10 +10.07 +3.93hydroxyethyl)amino]- red reflexes 2-nitrobenzene.HCl (1.200 g) 351-amino-5-chloro-4- 7.0 cherry-red +20.35 +24.84 +7.43[(2′,3′-dihydroxy- propyl)amino]-2- nitrobenzene (1.300 g) 361-amino-2-[(2′- 10.0 red-orange +29.98 +34.15 +23.20hydroxyethyl)amino]- 5-nitrobenzene (0.980 g) 37 4-[(2′-hydroxyethyl)-0.4 orange +51.18 +30.12 +59.68 amino]-3-nitro-1- methylbenzene (0.980g) 38 4-[(2′-hydroxyethyl)- 6.2 ruby-red +30.91 +48.81 +25.69amino]-3-nitro- phenol (0.990 g) 39 2-amino-6-chloro-4- 4.7 brown-violet+17.74 +15.06 +4.19 nitrophenol.HCl (1.120 g) 40 2-chloro-6-ethyl- 7.5red +29.73 +38.89 +23.40 amino-4-nitro- phenol (1.080 g) 412,5-diamino-6-nitro- 6.5 orange +39.10 +37.92 +40.11 pyridine (0.770 g)42 1-amino-4-[di(2′-hy- 4.8 brown with +18.76 +9.46 +3.08droxyethyl)amino]- red reflexes 2-nitrobenzene.HCl (0.60 g) and 4-[di-(2′-hydroxyethyl)- amino]-1-[(2′- methoxyethyl)- amino]-2-nitro- benzene(0.750 g)

Examples 43 to 51

[0044] Hair Colorants Component (A1) 0.488 g  of7-methoxy-4-nitro-2,1,3-benzoxadiazole  5.0 g of ethanol  4.0 g of decylpolyglucoside (aqueous solution; Plantaren ® 2000, supplied by Cognis,Germany)  0.2 g of disodium ethylenediaminetetraacetate hydrate to 100.0g water, demineralized Component (A2) X g of powdered amine and/orphenol as per Table 5.

[0045] The aforesaid mixture [component (A1)] was mixed uniformly withthe powder containing the amine or the phenol [component (A2)] at roomtemperature (20-25° C.) or with slight heating (35-40° C.)—optionally byadding a spatula tip-full of sodium acetate. If necessary, the pH wasadjusted to the desired value with sodium hydroxide or citric acid.

[0046] The ready-for-use hair colorant thus obtained was applied to thehair and uniformly distributed with a brush. After an exposure time of30 min at 40° C., the hair was rinsed with lukewarm water and thendried.

[0047] The amount of amine or phenol used and the resulting colorationsare summarized in the following Table 5. TABLE 5 Ex- ample Amine orPhenol Shade After Color values No. Used (amount in g) pH Dyeing L a b43 1,4-diamino-2- 4.7 violet +21.82 +19.70 +2.28 methylbenzene sulfate(0.55 g) 44 1,4-diamino-2-(2- 4.6 violet +17.75 +11.85 +1.25hydroxyethyl)ben- zene sulfate (0.63 g) 45 4-aminophenol 7.6 ruby-red+31.05 +46.43 +20.06 (0.273 g) 46 4-amino-3-methyl- 9.3 orange +44.84+32.42 +43.04 phenol [no amount given-Translator] 47 4,5-diamino-1- 9.9red +28.26 +34.16 +17.99 (2′-hydroxyethyl)- 1H-pyrazole sul- fate (0.600g) 48 2,4-diamino-1-(2′- 4.4 red-violet +28.41 +31.66 +11.88hydroxyethoxy)- benzene sulfate (0.660 g) 49 5-amino-2-methyl- 4.7 red+46.23 +48.47 +28.73 phenol (0.308 g) 50 3-aminophenol 4.2 red-orange+44.08 +51.80 +44.28 (0.273 g) 51 1,3-dihydroxy- 4.8 yellow +78.59 −0.89+62.74 benzene (0.275 g)

[0048] The L*a*b* values given in the preceding examples were determinedwith a Chromameter II color meter supplied by Minolta. The L valueindicates the brightness (namely the lower the L value the higher is thecolor intensity), whereas the a-value is a measure of the red content(namely the higher the a-value the higher is the red content). Theb-value is a measure of the blue content of the color, the blue contentbeing the higher the more negative is the b-value.

[0049] Unless otherwise indicated, all percentages in the present patentapplication are by weight.

1. Fiber-coloring agent (A) prepared by mixing two components (A1) and(A2), characterized in that component (A1) contains at least onecompound of formula (I)

wherein X denotes a halogen atom, a methoxy group or an ethoxy group; Ydenotes an oxygen atom, a sulfur atom or a selenium atom; R1 and R2 areequal or different and independently of each other denote hydrogen, ahalogen atom, a (C₁-C₄)-alkyl group, a halogen-substituted (C₁-C₄)-alkylgroup, a (C₁-C₄)-alkoxy group, a nitro group, an acetamido group or anNR^(a)R^(b) group, wherein the R^(a) and R^(b) groups are equal ordifferent and independently of each other denote hydrogen, a(C₁-C₄)-alkyl group, an optionally substituted aromatic carbon ring or a(C₁-C₄)-alkanecarbonyl group, or R^(a) and R^(b) together with thenitrogen atom form a heterocyclic (C₃-C₆) group; and component (A2)contains at least one compound selected from the group consisting ofamines, aminobenzenes and phenols.
 2. Agent according to claim 1,characterized in that the compound of formula (I) is selected from amongthe following 4-nitro-2,1,3-benzoxadiazoles,4-nitro-2,1,3-benzothiadiazoles and 4-nitro-2,1,3-benzoselenadiazoles:4-chloro-7-nitro-2,1,3-benzoxadiazole;4-bromo-7-nitro-2,1,3-benzoxadiazole;4-fluoro-7-nitro-2,1,3-benzoxadiazole;4-methoxy-7-nitro-2,1,3-benzoxadiazole;4-ethoxy-7-nitro-2,1,3-benzoxadiazole;4-chloro-5,7-dinitro-2,1,3-benzoxadiazole;5,7-dichloro-4-nitro-2,1,3-benzoxadiazole;5,7-dibromo-4-nitro-2,1,3-benzoxadiazole;7-chloro-4-nitro-5-diethylamino-2,1,3-benzoxadiazole;5-amino-7-chloro-4-nitro-2,1,3-benzoxadiazole;7-chloro-4-nitro-5-(1-piperidinyl)-2,1,3-benzoxadiazole;4-chloro-7-nitro-2,1,3-benzothiadiazole;4-bromo-7-nitro-2,1,3-benzothiadiazole;4-methoxy-7-nitro-2,1,3-benzothiadiazole;4-ethoxy-7-nitro-2,1,3-benzothiadiazole;4-chloro-5,7-dinitro-2,1,3-benzothiadiazole;4-bromo-5,7-dinitro-2,1,3-benzothiadiazole;4,5-dichloro-7-nitro-2,1,3-benzothiadiazole;5,7-dichloro-4-nitro-2,1,3-benzothiadiazole;4,5-dibromo-7-nitro-2,1,3-benzothiadiazole;5,7-dibromo-4-nitro-2,1,3-benzothiadiazole;4,6-dichloro-5,7-dinitro-2,1,3-benzothiadiazole;4,6-dibromo-5,7-dinitro-2,1,3-benzothiadiazole;5-chloro-7-fluoro-4-nitro-2,1,3-benzothiadiazole;5-anilino-7-bromo-4-nitro-2,1,3-benzothiadiazole;5-amino-7-chloro-4-nitro-2,1,3-benzothiadiazole;7-bromo-5-(diethylamino)-4-nitro-2,1,3-benzothiadiazole;4-chloro-5-methyl-7-nitro-2,1,3-benzothiadiazole;4-bromo-5-methyl-4-nitro-2,1,3-benzothiadiazole;7-bromo-5-(bromomethyl)-7-nitro-2,1,3-benzothiadiazole;N-(7-chloro-4-nitro-2,1,3-benzothiadiazole-5-yl)acetamide;4-chloro-7-nitro-2,1,3-benzoselenadiazole;4-bromo-7-nitro-2,1,3-benzoselenadiazole;4-methoxy-7-nitro-2,1,3-benzoselenadiazole;4-ethoxy-7-nitro-2,1,3-benzoselenadiazole;5,7-dibromo-4-nitro-2,1,3-benzoselenadiazole;5,7-dichloro-4-nitro-2,1,3-benzoselenadiazole;7-bromo-5-methyl-4-nitro-2,1,3-benzoselenadiazole and7-bromo-5-(bromomethyl)-4-nitro-2,1,3-benzoselenadiazole.
 3. Agentaccording to claim 1, characterized in that the amine, aminonitrobenzeneand phenol are selected from among ethanolamine, 1,4-diaminobenzene;1,4-diamino-2-methylbenzene; 1,4-diamino-2-(2′-hydroxyethyl)benzene;1,4-diamino-2-(1′-hydroxyethyl)benzene;2,4-diamino-1-(2′-hydroxyethoxy)benzene; 2,4,5,6-tetraaminopyrimidine;hydroquinone; 5,6-diamino-2,4-dihydroxypyrimidine; 2,7-diaminofluorene;1-amino-2-naphthol; 2,3-dihydro-3-methyl-2-benzothiazolone hydrazone;2-aminophenol; 4,5-diamino-1-(2′-hydroxyethyl)-1H-pyrazole;4,5-diamino-1-benzyl-1H-pyrazole; phenol;4,5-diamino-1-[(4′-methylbenzyl)-1H-pyrazole; 4,5-diamino-1H-pyrazole;4,5-diamino-1-methyl-1H-pyrazole; 4,5-diamino-(1-isopropyl)-1H-pyrazole;N-(3-dimethylaminophenyl)urea;2-amino-4-[(2′-hydroxyethyl)amino]anisole; 1,3-diaminobenzene;1,3-di(2,4-diaminophenoxy)propane; 4-methylphenol; 4-aminophenol;4-amino-3-methylphenol; 5-amino-2-methylphenol; 3-aminophenol;1,3-dihydroxybenzene; 5-hydroxyindole;4-[(2′-hydroxyethyl)amino]-3-nitro-1-methylbenzene;4-[(2′-hydroxyethyl)amino]-3-nitrophenol;2-amino-6-chloro-4-nitrophenol; 2-chloro-6-ethylamino-4-nitrophenol;1-amino-2-[(2′-hydroxyethyl)amino]-5-nitrobenzene as well as the2,5-diaminonitrobenzenes, for example1-(2′-hydroxyethyl)amino-2-nitro-4-[(di-(2′-hydroxyethyl)amino]benzene;1-amino-4-[di(2′-hydroxyethyl)amino]-2-nitrobenzene;4-[di(2′-hydroxyethyl)amino]-1-[(2′-methoxyethyl)amino]-2-nitrobenzene;4-[ethyl-(2′-hydroxyethyl)amino]-1-[(2′-hydroxyethyl)-amino]-2-nitrobenzene;1-amino-5-chloro-4-[(2′,3′-dihydroxypropyl)amino]-2-nitrobenzene and2,5-diamino-6-nitropyridine.
 4. Agent according to one of claims 1 to 3,characterized in that the compounds of formula (I) and the amines,aminonitrobenzenes and/or phenols are contained in the dye carrier[component (A1) or component (A2)] in a total amount from 0.02 to 20 wt.%.
 5. Agent according to one of claims 1 to 4, characterized in that thecompounds of formula (I) and the amines, aminonitrobenzenes and/orphenols are contained in the ready-for-use hair colorant (A) in a totalamount from 0.01 to 10 wt. %.
 6. Agent according to one of claims 1 to5, characterized in that it contains additionally from 0.02 to 20 wt. %of a physiologically innocuous, direct dye selected from the groupconsisting of cationic and anionic dyes, disperse dyes, nitro dyes, azodyes, quinone dyes and triphenylmethane dyes.
 7. Agent according to oneof claims 1 to 6, characterized in that the ready-for-use colorant (A)has a pH from 3 to
 12. 8. Agent according to one of claims 1 to 7,characterized in that it additionally contains an oxidation dyeprecursor.
 9. Agent according to one of claims 1 to 8, characterized inthat it is mixed with an oxidant before use.
 10. Agent according to oneof claims 1 to 9, characterized in that it is a hair-coloring agent. 11.Hair-dyeing method whereby the ready-for-use coloring agent (A) isprepared immediately before use by mixing two components (A1) and (A2),optionally with addition of sodium acetate, and is then applied to thehair and allowed to act for 5 to 60 minutes at a temperature of 20 to50° C., the hair then being rinsed with water, optionally washed with ashampoo, and then dried, characterized in that a coloring agent (A)obtained by mixing two components (A1) and (A2) according to one ofclaims 1 to 10 is used.
 12. Multicomponent kit for dyeing hair,consisting of a preparation of component (A1) according to one of claims1 to 10 and of a preparation of (A2) according to one of claims 1 to 10and optionally of an agent for adjusting the pH.
 13. Use of acombination of at least one compound of formula (I)

wherein X denotes a halogen atom, a methoxy group or an ethoxy group; Ydenotes an oxygen atom, a sulfur atom or a selenium atom; R1 and R2 areequal or different and independently of each other denote hydrogen, ahalogen atom, a (C₁-C₄)-alkyl group, a halogen-substituted (C₁-C₄)-alkylgroup, a (C₁-C₄)-alkoxy group, a nitro group, an acetamido group or anNR^(a)R^(b) group, wherein the R^(a) and R^(b) groups are equal ordifferent and independently of each other denote hydrogen, a(C₁-C₄)-alkyl group, an optionally substituted aromatic carbon ring or a(C₁-C₄)-alkanecarbonyl group, or R^(a) and R^(b) together with thenitrogen atom form a heterocyclic (C₃-C₆) group, and at least onecompound selected from the group consisting of amines,aminonitrobenzenes and phenols, for dyeing keratin fibers.